Permanent finish vegetable material and process of producing same



hand A... 17, 1928.

UNITED STATES rA'ranrorr-lcs.

ALBERT BODMER, OF WATTWIL, SWITZERLAND, ASSIGNOR T HEBERLEIN PATENT CORPORATION, OF NEW YQBK, N. Y., A QORPOBATION OF NEW YORK.

PERMANENT FINISH VEGETABLE MATERIAL AN D PROCESS Q1! PRODUCING- No Drawing. Application filed April 11, 1923, Serial No. 631,874, and 111 Germany April 15, 1928.-

This' invention relates to permanent finish vegetable material and process of producing same, such for example as ermanent finlshes produced on cotton goo s by efi'ectmg a 5 chemical structural change in the fibres.

been produced by processes hereinafter referred to.

The object of the present invent1on 1s to improve the character and quality of permanent finish goods and also the process of producing same. According to the preferred manner of practicing the present nventron, the hydrolyzation of the fi res b the act1on of a concentrated mineral acid w ich 1s used in producing these permanent finlshes, is stabilized so that the acid may be allowed 7 to act on the oods for a greater length of time so as to e ect a more gradual and greater penetration of the goods and hence a more thorou h and uniform conversion of the fibres, and with much less risk of produc ing detrimental effects, damage or destruction of the goods.

The invention consists in the novel process or processes hereinafter described, by way of example, inaccorda'nce with certain wa s of carrying out .the same, and also in t e 7 resulting fabrics. The invention will be particularly pointed out in the appended claims.

In order that the sco e of the use and application of'the invent1on to ods for the production of permanent fimshes may be more readily understood, I will first refer to some of the rior processes for producing I permanent finishes and to which this inven- 1 stitutes an im rovement.

' granted to George's Heberlein, there wastion is applicable and upon which it con- In United tates Patent No. 1,141,872,

described the process of treating cotton fabric to produce permanent wool-likeeffects by subjecting the fabric to two treatments, one a mercerizing treatment such as with caustic soda, and the other a treatment with concentrated sulfuric acid of less than 51 B. It was described in that patent s ecification that if cotton fabric which has een mercerized and also preferably bleached, be subjected to the action of sulfuric acid of parenc from 49 to somewhat under 51 B. (the best action being obtained between 49 and 50% B.), the me'rcerizing lustre disappears'and the fabric ap ears fuller softer and more wool-like an is generally imroved, so as to take on the character of ne thin wool muslin.

It was also pointed out in United States Patent No. 1,439,514, to Georges Heberlein, that this wool-like effect could also be obtained if in said process there was substituted for the sulfuric acid, other reagents, including other strong mineral acids, such for example as hydrochloric acid of the specific gravity of 1.19 at low temperature,

' or nitric acid of 43 to 46 B., or phosphoric acid of 55 to 57 B.

It was also pointed out in United States Patent No. 1,144,655, granted to Georges Heberlein, that when the cotton fabric was subjected to the mercerizing or caustic soda treatment and the sulfuric acid treatment, utilizing the acid at'a higher concentration than that used for the wool effect, i. e., over 50 B., for example, about 54 B., then the said transparent permanent effect or permanent or andie would result.

It was urther pointed out in the United States patent to Eduard Heberlein, No. 1,265,082, that the permanent transparent effect could be obtained if the cotton fabric was treated. for a suflicient period with the caustic alkali cooled below 0 (1., and of such concentration as would mercerize the cotton at the ordinary temperature. That is to say, of at least 15 B. specific gravity; and that if in-conjunction with the treatment of' said, cold caustic alkali the fabric was also treated with the last mentioned sulfurio' acid treatment, a more enhanced trans- Woal'd result. Furthermore, it was pointe out in United States Patent No. 1,439,519, to Eduard Heberlein, that when the treatments set forth in said Patent 1,265,082 (1. e., a treatment with the caustic soda at a temperature below 0 0., or said.

treatment inconjunction with a treatment with the sulfuric acid of over 50 Baum, and preferably about 54 Baum) were carried out upon yarns or webs constituted of threads whose fineness does not exceed English yarn No. 80, permanent linen-like effects would be produced-,' It was also point} enhanced linen-like effects would be produced if in conjunction with the'acid treatthe hydrolyzing action that water exerts in ment and the cold caustic soda treatment the goods were also subjected to the caustic soda or mercerizing treatment at normal tem erature. Among other'Letters Patent disc osing processes producing permanent finishes and permanent finish products and upon which the present invention is an imrovement, I might mention the following, 1. e., 1,288,884, 1,258,225, 1,285,738, 1,392,264 and 1,392,265.

In the practicing or execution of these processes it has been found that due to the detrimental effects that these concentrated acids will quickly produce on the goods if not very accurately controlled, it was very important to accurately measure and limit the action of the acid in order to safeguard the fabric. It was therefore found to be necessary to interrupt or arrest the reaction suddenly after an interval of time that had to be strictly adhered to,-inasmuch as an excess of the action always resulted in an undesirable hydrolyzation or decomposition of the cellulose. This decomposition even makes itself evident during the swelling reactions. The consequences of any excess of this hydrolytic decomposition of the cel lulose made themselves evident, on the one hand, in the form of a diminution of the toughness or strength of the fibre, and on the other hand, in the form of an excessive hardening of the fibres.

Now I have discovered that the reaction of the concentrated mineral acids on these materials, which is quite aggressive, may to some degree be regulated and stabilized by the use of suitable heterocyclic compounds miscible with the particular mineral acid used, -as for example sulfuric acid, and thereby itis possible to somewhat increase the strength of the acid used in the sense of decreasing the proportion of water thereto and so decreasing the water acid ratio and the presence of acid. Furthermore, I have discovered that the preferred heterocyclic compounds are heterocyclic bases such as pyridine, etc. I have discovered that in a surprising. manner, for example, salts'of pyridine, quinolin, their homologues and derivatives, manifest the property, when added to mineral acids, of stabilizing the swelling action of the fibres due to the action of the acid i. e., of holding back the hydrolytic decomposition of the cellulose so that the swelling may be completely-realized without injurious hydrolyza'tion. These deterring agents, I have found, exert a specific action in partially and temporarily neutralizing a portion of the acid without atthe same time permanently inhibiting its action as would a strong alkali. I have found that certain of the heterocyclic compounds such as salts of the 'heterocyclic bases and their derivatives, particularly pyridine and quinolin,

their homologues and derivatives, produce a toning down of, or a sort of retarding effeet upon the reaction during the treatment of the goods with the acid, in the sense that by their presence they retard the rate of re action and have thereby the great commercial advantage of allowing much more time in which to adjust and regulate the precise degree of action required to attain the most desirable appearance effects on the surface of the fibre undergoing treatment, While still enabling the core or'center of the fibre or yarn to be thoroughly treated to attain more desirable qualities in thefabric in addition to the more desirable appearance effects.

In this manner it is possible to prolong the duration of the action to fifty times the normal periodwithout injury to the goods being 1processed or ennobled; and it is also possib e to safely use more concentrated acids for a given finish. If, for example, a mixture consisting of one part of pyridine and four parts of sulfuric acid of 66 Baum is allowed to act upon previously bleached mercerized muslin fabric, the latter after about four minutes, comes to have a trans parent appearance, inconnection with which a remarkable softness of effect is to be noted. .Again, if for example, We operate'in such a way that a suitable mercerized cotton fabric is subjected for 5 minutes to the. action of a mixture of 1 part of pyridine and 9 parts of sulfuric acid of 565 Baum, a pronounced soft wool effect is obtained with a sort of discernible bloom or overlaid opalescence which slightly lights up the dull tone of the. wool-like effect. The improvevment is therefore greater smoothness and softness to the touch and a slight lighting up of the dull tone wool-like effect. The proportion of acid and pyridine in the mixture may vary Within Wide limits, according to the desired effect and the goods to be worked up.

According to the present invention it is also feasible to thoroughly improve very compact fibrous structures, such for example as coarse yarns, to produce the transparent and the wool-like effects, which heretofore has not been possible as regards transparent effects and has not been possible with some of the acids as regards wool-like effects, since in the treatment of such coarse yarns either a merely superficial change took place, or in' case the action of the acid was allowed to continue for a sufficient duration to cause greater penetration of the yarn, then partial containing the heterocyclic base without emwit , Patent 1,144,655.

ployment of any caustic soda or mercerizing treatment as heretofore mentioned for the production of linen-like effects. For example, if one takes yarns or webs constituted 'of threads whose fineness does not exceed En lish yarn No. 80 and treats such goods the concentrated mineral acid containing the heterocyclic base, the linen-like effect is produced. But superior linen-like effects will be obtained/ if the mercerization treatment at normal temperature is used in conjunction with the treatment with the mixed acid and the heterocyclic base, in the. same manner as the normal mercerization was used in conjunction with the acid according to the said Patent 1,439,519, or said For the treatment of coarse fabrics for the production of linenlike effects sulfuric acid and pyridine may be used in substantially the same strength and proportions as above given by way of example for the production of transparent effects, i. e., sulfuric acid at 66 Baum and pyridine in the proportion of one part of pyridine to four parts of the acid.

I am aware of the fact that it has been proposed (see German Patent No. 139,669 to A. Wohl, and Schwalbe, Chemie de Cellulose, 1911, p. 320) to use a heterocyclic base in producing cellulose acetate by means of "acetyl chloride. But that proposed use of a heterocyc lic base in the presence of an organic acid chloride for the purpose of con verting chopped or pulverized paper directly into cellulose acetate, is quite a different matter from that of the present invention relating to the ennobling or finishing of fibrous goods (yarns and webs) to produce permanent effects thereon. According to the present inventlon, in all cases in which concentrated mineral acids have heretofore been employed for produc ing permanent effects in fibrous materials, such for example as in the production of said transparent organdie, wool-like effects, linen effects, etc., the acid may advantageously be used in the presence of a. suitable heterocyclic compound, such for example, as the salts of the heterocyclic bases miscible with the acid, or, in-other words, the conc'entrated acids of the strengths heretofore used may be replaced by a mixture of said acid and a heterocyclic base, in which case the acid at even greater concentration may be allowed to act for amuch longer period sirable in all instances to wash the goods For the purpose of this invention, suitable I heterocycliccompounds or heterocyclic bases are such heterocyclic compounds 'or bases as have pyridin ciaracteristics for the purpose, and as are miscible in the respective mineral acids with which they may be -used for producing the particular permanent finish. included for example various heterocyclic compounds or bases containing a pyridin nucleus. For example, in the case of the use of sulfuric acid as the strong mineral acid, such hcterocyclic compounds or bases \may be used as have pyridin characteristics for the purpose, and as are miscible in the sulfuric acid, and'in the case of nitric acid such heterocyclic compounds or bases would be used as have pyridin characteristics for the purpose, and as are miscible in nitric acid.

I Also for the purpose of this invention, suitable mineral acids are those that are capabl-c of dissolving cellulose fibres so as to produce a permanent efi'ect without detrimental etfect, such for example as the acids mentioned in the above set forth United States patents.

Such features of my invention as are not herein claimed are covered by my copending application Serial No. 631,745, filed April 12, 1923, for ve etable yarns and fabrics with wool-like e ects. I

VYhile I have described my invention with particularity, by way of example, with reference to certain preferred specific deterrin or stabilizing reagents, it will be understoo by those skilled in the art, after understanding my invention, that other reagents may be substituted without departing from the spirit or scope of the invention, and I aim in the appended claims to cover the use of all such reagents and processes as come within the scope of the invention,

What I claim as new and desire to secure by Letters Patent, is: I

1. Method of treating vegetable fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to give to the material a permanent finish, which method comprises treating the material with a concentrated cellulose dissolving mineral acid in the presence of a suitable heteroeyclic base containing a pyridin nucleus and which will stabilize the reaction by retarding its rate without inhibiting the ultimate desired extent of the reaction.-

2. Method of treating vegetable fibrous material (yarns and goods made therefrom) Among these compounds or bases are.

to chemically structurally alter the fibres to give to the material a permanent finish,'

8 material (yarns and goo to chemically structurally alter the .fibres to. give to the material a permanent finish,-

lie base havingl pyridin characteristics for"- made therefrom) which method comprises" treating the material with a concentrated cellulose dissolving 1 l0 mineral acid containing pyridine for stabilize terial to a plurality of chemical treatments,

ing the reaction.

4. Method of treating vegetable) fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to give to. the material a permanent" finish, which method comprises treating-the material 'with a concentrated cellulose dissolving mineral acid in the presence of a heterocyclic compound having pyridin characteristics 20 for the purpose and which is miscible with the acid and will stabilize the reaction.

5. Method of treating vegetable fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to 2 give to the material a permanent finish, which method comprises treating the material with a concentrated sulphuric acid in the presence of a heterocyclic compound containing a pyridin nucleus and which will sta bilize the reaction by retarding the rate of manently inhibiting the action of the acid.

6. Method of treating vegetable fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to give to the material .a permanent finish,

which method comprises treating, the material with concentrated sulfuric acid containin a salt of a heterocyclic base havingpyii in characteristics for the purpose, whic salt 'is miscible with theacid and which will stabilize the reaction.

7. Method of treating vegetable fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to give to the material a permanent finish,

which method comprises treating the mate-.

which method comprises subjecting the ma-' terial to a plurality of chemical treatments, one a treatment with caustic alkali which will chemically structurally change the fibres, and the other a treatment with a suitable concentrated strong mineral acid in the presence of a suitable heterocyclic base havmg pyridin characteristics for. the purpose, during which last treatment said heterocyclicvegetable fibrous will hydrolyzationof the cellulose without per-' base will stabilize the reaction retardingthe; rate of hydrolyzation' of the cellulose w1thout permanently inhibiting the action of the acid to produce, inpconjunctionwith said other treatment, sald permanent finish.

vegetable fibrous '9. Method of treating d h f s ma e t ere rom material (yarns and goo ,to chemically structurally alter the fibres to give to the material a permanent finish, wh1ch method comprises subjecting the ma one a treatment with caustic alkali which will chemically structurally change the fibres, and another a treatment with concentrated sulturicacid'in the presence of a suitable heterocyclic base having pyridin characteristics for the purpose,fand which differently chemically f structurally change the fibres, during which last treatment said hoterocyclic base will stabilize the reaction retarding the rate of hydrolyzation of the cellulose without permanently inbibiting the action of the acid'to produce, in conjunction with said other treatment, said permanent finish, the material being subjected to one of said treatments after the other, and after'the acid treatment washing the material.

10. Method of producing permanent linenlike efi'ects .in vegetable fibrous. material .(yarns and goods made therefrom) whichmethod comprises taking for treatment such material constitutedof. threads whose fineness does'notexceedv English yarn No. 80,

and treating such material with concentrated sulfuric acid in the-presence of a heterocyclic compound having pyridin characteristics for the purpose,'and which will stabilize the reaction lay-retarding the rate of hydro:

lyzation of the cellulose without permanently inhibiting the action of the ac1d.-

'11. Method of producing permanent linenlike efiects in. vegetable fibrous material (yarns and goods made therefrom) which method comprises taking for treatment such ness does not exceed English yarn No. 80,

- and subjecting said material to a plurality of pose during which last treatment said heterocyclic base will stabilize the reaction by retarding the rate of hydrolyzation of the cellulose without permanently inhibiting the action of the acid to produce, in conjunction with said other treatment, said linen-like efiect.

Qmaterial constituted of threads whose fine- .the presence of a suitable heterocyclic base, having pyridine characteristics for the pur- 12. Method of treating vegetable fibrous material (yarns and goods made therefrom) to chemically structurally alter the fibres to give to the material apermanent finish,

which method comprises treating the material with a concentrated cellulose dissolving mineral acid containing a heterocyclic-compound having pyridin characteristics for the purpose and which will stabilize the reaction,

the strength ofthe acid and the duration of the treatment of the material therewith being such that without the heterocyclic compound the material would be damaged by the action of said acid thereon.

13. Vegetable fibrous material (yarns and goods ,made therefrom) constituted of threads whose fineness does not exceed En lish yarn No. 80, and having a permanent linen-like effect produced by chemical treatment of the material, which treatment comprises a treatment with concentrated sulfuric acid containing asuitable heterocyclic goods made therefrom) constituted of threads whose fineness does not exceed Engtreatment of the goo s,

cfimpound having pyridin characteristics for lish yarn No. 80, and having a permanent I finish produced by chemical treatment of the material, which treatment comprises a treatment with a concentrated mineral acid containing a suitable heterocyclic compound having pyridin characteristics for the .purpose, and a treatment with caustic alkali.

15. LA cotton fabric "the fibres of which have been chemicall altered by a chemical which treatment comprises a treatment with concentrated mineral acidin the presence of a suitable heterocyclic compound having pyridin characteristics for the purpose and a treatment with caustic alkali, and having a resulting permanent which is softer than would be possible by treatment of the original cotton fabric with said alkali and mineral acid without the heterocyclic compound.

testimony whereof I have name to this specification.

' ALBERT BODMER.

signed my 

